EP2490235B1 - Elektronentransportierende Titanoxidschicht - Google Patents

Elektronentransportierende Titanoxidschicht Download PDF

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EP2490235B1
EP2490235B1 EP11154603.2A EP11154603A EP2490235B1 EP 2490235 B1 EP2490235 B1 EP 2490235B1 EP 11154603 A EP11154603 A EP 11154603A EP 2490235 B1 EP2490235 B1 EP 2490235B1
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mol
equivalents
mixture
alkyl groups
process according
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French (fr)
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EP2490235A1 (de
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Afshin Hadipour
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Interuniversitair Microelektronica Centrum vzw IMEC
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Interuniversitair Microelektronica Centrum vzw IMEC
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Priority to EP11154603.2A priority Critical patent/EP2490235B1/de
Priority to JP2012008142A priority patent/JP5845097B2/ja
Priority to US13/358,929 priority patent/US20120207947A1/en
Priority to KR1020120014438A priority patent/KR101876575B1/ko
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
    • B01J2/02—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by dividing the liquid material into drops, e.g. by spraying, and solidifying the drops
    • B01J2/06—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by dividing the liquid material into drops, e.g. by spraying, and solidifying the drops in a liquid medium
    • B01J2/08—Gelation of a colloidal solution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/04—Coating on selected surface areas, e.g. using masks
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
    • H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
    • H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50—Photovoltaic [PV] devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
    • H10K85/211—Fullerenes, e.g. C60
    • H10K85/215—Fullerenes, e.g. C60 comprising substituents, e.g. PCBM
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to the field of organic optoelectronics.
  • Organic solar cells typically at least comprise an anode, a cathode and an organic active layer in between said anode and said cathode. At least one of said anode and said cathode is transparent. When the organic solar cell is exposed to light, the active layer absorbs part of said light to generate both electrons and holes within said active layer. The holes are then collected at the anode and the electrons at the cathode. If the anode allows electrons to pass through it, or if the cathode allows holes to pass through, the performance of the solar cells decreases since those charges are lost by recombination. lt is therefore very important that only holes are allowed to pass through the anode and that only electrons are allowed to pass through the cathode.
  • HTL hole transporting layer
  • ETL electron transporting layer
  • evaporated materials such as lithium fluorid (LiF), ytterbium (Yb) or samarium (Sm) are used. These materials have a low work-function and they oxidize very easily.
  • solution-born ETLs and HTLs needed to be developed. Since a solution for a solution-born HTL already exists (PEDOT:PSS), the next step is to find a solution-born ETL.
  • ZnO zinc oxide dispersion
  • TiO x titanium oxide
  • All those ETL layers need some post-treatments such as thermal annealing (e.g. up to 250°C for sintering the ZnO nano-particles), processing in air (e.g. the TiO solution is taken out into air for hydrolysis and condensation processes) or UV exposure (under UV, oxides generates some extra holes.
  • thermal annealing e.g. up to 250°C for sintering the ZnO nano-particles
  • processing in air e.g. the TiO solution is taken out into air for hydrolysis and condensation processes
  • UV exposure under UV, oxides generates some extra holes.
  • the increase of hole concentration leads to higher electron mobility and increases the conductivity) to improve their conductivity.
  • Heeger et al. describe a polymer photovoltaic cell using a solution-based titanium oxide as an optical spacer in which the TiO x layer is obtained by a sol-gel procedure involving the mixing of 5 ml titanium (lV) isopropoxide with 20 ml 2-methoxyethanol and 2 ml ethanolamine at room temperature. The starting materials are injected in this order. After one hour stirring at room temperature, the mixed solution is heated at 80°C for an hour, followed by heating to 120°C for another hour. During all these procedures, the mixture is kept under N 2 atmosphere and the solution is stirred continuously at 600-800 rpm.
  • the final step after cooling to room temperature is to add 10 ml of an alcohol selected from methanol, ethanol or isopropanol to the mixture.
  • an alcohol selected from methanol, ethanol or isopropanol
  • the TiOx sol-gel of Heeger is spincasted in air on top of an active layer.
  • the sample is then annealed at 80°C for 10 min in air before that an aluminium electrode is deposited.
  • This procedure of thermal annealing requires heating which is energy demanding.
  • thermal annealing in air of the deposited film is not only energy demanding but also dangerous for the organic active layer (organic materials used as active layer, can be oxidized in air leading to loss of all their opto-electronics properties).
  • the ETL layer does not require any thermal annealing steps.
  • an efficient ETL titanium oxide layer can be obtained in an energy efficient way since no heating of the sol-gel solution and no thermal annealing (let alone thermal annealing in air) of the spin casted film is required for hydrolysis and condensation processes.
  • the present invention relates to a process for making a solution for forming a titanium oxide, e.g. TiO x , sol-gel layer. This process is preferably performed under inert atmosphere.
  • said process involves the mixing of:
  • R 1 is preferably (CH 2 ) 2 -Y.
  • Y is preferably OH.
  • N(R 1 )(R 2 )(R 3 ) is ethanolamine.
  • titanium oxide precursors include, but are not limited to, titanium tetraisopropoxide, titanium tetrabutoxide, titanium tetraethoxide, titanium tetraoxychloride, titanium tetrachloride and titanium n-propoxide.
  • the titanium oxide precursor is preferably a titanium alkoxide, preferably a titanium (IV) alkoxide of general formula (II): Ti(OR) 4 (II) wherein R is selected from C 1 -C 4 linear alkyl or C 3 -C 4 branched alkyl chains. Most preferably, the titanium oxide precursor is titanium (IV) isopropoxide.
  • water miscible alcohol an organic compound comprising at least one alcohol function and which is soluble in water in all proportions at room temperature and 1 atm.
  • the water miscible alcohol preferably has the general formula (III): R-OH (III) wherein R is selected from C 1 -C 3 linear alkyl and C 3 branched alkyl groups.
  • said alcohol is ethanol.
  • the acid can be any acid but is preferably an organic acid.
  • the pKa of the acid may for instance be from -2 to 12. More preferably, it has the general formula (IV): R-COOH (IV), wherein R is selected from C 1 -C 4 linear alkyl and C 3 -C 4 branched alkyl groups.
  • step (b) said first mixture is further mixed with a carbohydrate.
  • a carbohydrate is a sugar alcohol, preferably, said sugar alcohol may have 6 carbons and most preferably it is D-sorbitol.
  • Adding a carbohydrate is advantageous because it increases the adherence of the layer to a substrate. It is particularly advantageous in the reverse devices (see Fig. 2 ) since the titanium oxide layer must there be deposited on the inorganic conductive oxide (e.g. ITO) layer on which adherence is typically problematic.
  • ITO inorganic conductive oxide
  • a surfactant may be added to the mixture at any step of said process. This is advantageous as it increases the ability of the solution to wet a substrate.
  • the solution obtained after step (e) may be clear.
  • it is preferably not turbid. Turbid solutions have been shown by the inventor to lead to lower efficiencies and to devices only showing maximal performance after photoactivation (see Fig. 5 ).
  • Titanium oxide precursor from 0.5 to 2 mol. equivalents, preferably from 0.8 to 1.2 mol. equivalents.
  • this process is performed at room temperature, e.g. from 18 to 25°C.
  • this process is performed under an inert atmosphere.
  • it may be performed in a glove box filled in with an inert gas such as N 2 or Ar.
  • the process may further comprise the step of
  • said mixing steps are performed at 300 to 1400 rpm.
  • the pH of the solution obtained after step (e) is from 8.0 to 10.0
  • the application relates to a solution obtainable by the process of any embodiment of the first aspect optionally followed by a dilution in a water miscible alcohol.
  • This dilution can for instance be from two-fold to twenty-fold, preferably from five-fold to fifteen-fold (by volume). It is preferred to dilute the solution before to perform step (b) of the third aspect.
  • the application relates to a process for making a device, said process comprising the steps of:
  • said process according to the third aspect may be performed at room temperature.
  • the solution of the second aspect is allowed to age at room temperature for at least 90 minutes after step (e) of the first aspect before to perform said step of diluting said solution and/or of applying said (optionally dilute) solution to said substrate.
  • the process of the third aspect does not comprise an annealing step, an oxygen treatment or a photo-doping with UV light after step (b) of the process for making a device according to the third aspect.
  • step (b) is performed via spin coating, spray coating or inkjet printing.
  • the application relates to a device.
  • the device is preferably an opto-electronic device. More preferably, it is a photovoltaic device and/or an organic opto-electronic device. Most preferably, it is an organic photovoltaic device.
  • the device of the fourth aspect is obtainable by a process of the third aspect of the present invention.
  • the device according to the fourth aspect comprises a titanium oxide layer, e.g. a titanium suboxide layer.
  • this titanium oxide layer serves as an electron transporting layer.
  • the ratio oxygen to titanium in the titanium oxide layer, [d1] typically takes values ranging from 1.1 to 1.9.
  • the device of the fourth aspect is an organic photovoltaic cell, it typically comprises a transparent substrate (e.g. glass), a transparent anode on top of said transparent substrate (the anode is typically indium tin oxide (ITO)), an HTL on top of said anode, an active layer on top of said HTL, an ETL on top of the active layer and a cathode on top of the ETL (the cathode can for instance be an Al or a Ag cathode).
  • ITO indium tin oxide
  • the cathode can for instance be an Al or a Ag cathode.
  • the device may be a "reversed" device where the ETL is on top of the cathode (e.g.
  • ITO is here used as a cathode), where the active layer is on top of the ETL, where the HTL is on top of the active layer and where the anode is on top of the HTL (the anode can here be e.g. a Au, Al or Ag layer).
  • the device according to the fourth aspect further comprises a cathode and an anode.
  • said cathode is an aluminium cathode.
  • said electron transporting layer has a thickness of from 5 nm to 40 nm, preferably from 10 to 35 nm, more preferably from 20 to 30 nm.
  • said electron transporting layer comprises a surfactant.
  • said electron transporting layer comprises a carbohydrate as defined in any embodiment of the first aspect the present invention.
  • Coupled should not be interpreted as being restricted to direct connections only.
  • the terms “coupled” and “connected”, along with their derivatives, may be used. It should be understood that these terms are not intended as synonyms for each other.
  • the scope of the expression “a device A coupled to a device B” should not be limited to devices or systems wherein an output of device A is directly connected to an input of device B. It means that there exists a path between an output of A and an input of B which may be a path including other devices or means.
  • Coupled may mean that two or more elements are either in direct physical or electrical contact, or that two or more elements are not in direct contact with each other but yet still co-operate or interact with each other.
  • an element described herein of an apparatus embodiment is an example of a means for carrying out the function performed by the element for the purpose of carrying out the invention.
  • titanium suboxide as used in disclosing the present invention, means a titanium oxide with a O/Ti atomic ratio between 1 and 2, preferably between 1.1 and 1.9. Typically, said titanium suboxide has electron-conducting properties.
  • a 4 ml bottle was placed on a stirring plate (600 rpm) in a glove box kept at room temperature under inert atmosphere. 1 ml of ethanol was mixed with 3 mg of D-sorbitol until all sorbitol was dissolved. The resulting mixture (mixture X) was clear.
  • Example 2 fabrication of a conventional cell
  • a stack made of a glass substrate 6, an ITO anode 5, a HTL 4 and an active medium 3 was first prepared. Then, in a glove box under N 2 atmosphere, the solution of example 1-a was diluted fivefold with ethanol and spin coated onto the active layer 3 made of a poly(3-hexylthiophene): phenyl-C 61-butyric acid methyl ester (P3HT:PC60BM) bulk heterojunction. The obtained titanium oxide layer 2 was not exposed to any further treatment. A cathode 1 was finally evaporated onto the titanium oxide layer. The resulting device had the following structure: ITO/PEDOT/P3HT:PC60BM (250 nm)/titanium oxide(10 nm)/Al(100 nm).
  • a 4 ml bottle was placed on a stirring plate (600 rpm) in a glove box kept at room temperature under inert atmosphere. 1 ml of ethanol was mixed with 3 mg of D-sorbitol until all the sorbitol was dissolved. The resulting mixture (mixture X) was clear.
  • the same device as for example 2 was built except that the titanium oxide layer 2 was replaced by an evaporated Yb layer 2.
  • the resulting device had the following structure: ITO/PEDOT/P3HT:PC60BM (250 nm)/Yb (50 nm)/Al (100 nm).
  • a stack made of a glass substrate 6 and an ITO cathode 5 was first prepared. Under inert atmosphere (N 2 , glove box), a titanium oxide solution according to example 1-a but diluted fivefold with ethanol was then spin-coated on said ITO cathode 5 and allowed to dry without exposition to any further treatment, thereby forming titanium oxide gel 2.
  • An active layer 3 composed of a mixture of poly(3- Hexylthiophene) and phenyl-C 61-butyric acid methyl ester was then spin-coated on said titanium oxide gel 2. The active layer 3 was allowed to dry.
  • a HTL 4 was then spin-coated onto said active layer 3 and allowed to dry.
  • the resulting device had the following structure: ITO/titanium oxide(10-12 nm)/P3HT:PC60BM(250 nm)/PEDOT/ Al(100nm).
  • the squares correspond to the current density vs voltage measures made in the dark while the circles correspond to measurements made under exposure to UV irradiation.
  • the fill factor for the device was 62.0% and the efficiency of the device was 3.63%.
  • Fig. 5 it is shown that when the turbid solution of comparative example 1 is used, the first measurement (before exposure, circles) shows a low quality solar cell with a low fill factor of 31.6% and a low efficiency of 0.66%. Only after exposure to UV light does the performance of the device improve.
  • the fill factor was at 45.5% and the efficiency was at 1.67% (upward oriented triangles).
  • the fill factor was at 49.8% and the efficiency was at 1.99% (downward oriented triangles).
  • the fill factor was at 50.1% and the efficiency was at 2.16% (diamonds).
  • the fill factor was at 50.1 % and the efficiency was at 2.17% (respectively leftward oriented triangles, rightward oriented triangles and hexagones).
  • Fig. 6 it is shown that the directly measured cell (i.e. when the cell was kept in the dark up to the time of the measurement) and the cell which was UV-exposed for 1 min before measurements attain a constant efficiency. This shows that when the solution was clear without aggregation (case of the solution of examples 1), photo-doping was not needed.

Claims (11)

  1. Verfahren zur Herstellung einer Lösung zur Bildung einer Titanoxid-Sol-Gelschicht, wobei das Verfahren vorzugsweise unter einer inerten Atmosphäre ausgeführt wird, wobei das Verfahren das Mischen von:
    - 0,5 bis 3,0 molaren Äquivalenten, vorzugsweise 1,0 bis 1,8 molaren Äquivalenten einer Säure;
    - 1,0 bis 5,0 molaren Äquivalenten, vorzugsweise 2,0 bis 2,6 molaren Äquivalenten Wasser;
    - 5,0 bis 20 molaren Äquivalenten, vorzugsweise 8 bis 13 molaren Äquivalenten eines wassermischbaren Alkohols,
    - 0,5 bis 2 molaren Äquivalenten, vorzugsweise 0,8 bis 1,2 molaren Äquivalenten eines Titanoxidvorläufers und
    - 2,5 bis 10 molaren Äquivalenten, vorzugsweise 4,0 bis 6,4 molaren Äquivalenten einer Verbindung der allgemeinen Formel (I)

            N(R1) (R2) (R3)     (I)

    beinhaltet, wobei R1 aus der Liste bestehend aus C1-C4 linearen Alkylgruppen und C3-C4 verzweigten Alkylgruppen ausgewählt ist, wobei jede Alkylgruppe optional durch eine Gruppe Y substituiert sein kann, die aus der Liste bestehend aus -NH2, -SH, -OH, -NR4R5, -SR', -OR" ausgewählt ist, wobei R4, R5, R' und R" aus der Liste bestehend aus C1-C4 linearen Alkylgruppen und C3-C4 verzweigten Alkylgruppen ausgewählt sind, wobei R2 und R3 unabhängig aus der Liste bestehend aus H, C1-C4 linearen Alkylgruppen und C3-C4 verzweigten Alkylgruppen ausgewählt sind, wobei jede Alkylgruppe optional durch eine Gruppe Y substituiert sein kann, die aus der Liste bestehend aus -NH2, -SH, -OH, -NR4R5, -SR', -OR" ausgewählt ist, wobei R4, R5, R' und R" aus der Liste bestehend aus C1-C4 linearen Alkylgruppen und C3-C4 verzweigten Alkylgruppen ausgewählt sind, wobei das Mischen folgende Schritte umfasst:
    a) Mischen der Säure mit dem Wasser, wodurch ein erstes Gemisch erhalten wird,
    b) Mischen des ersten Gemisches mit dem wassermischbaren Alkohol, wodurch ein zweites Gemisch erhalten wird,
    c) Mischen der Verbindung der allgemeinen Formel (I) mit dem zweiten Gemisch, wodurch ein drittes Gemisch erhalten wird,
    d) Warten über eine ausreichende Zeit, damit das dritte Gemisch Raumtemperatur erreicht, z.B. 10 bis 15 Minuten,
    e) Hinzufügen des Titanoxidvorläufers zu dem dritten Gemisch, wodurch die Lösung erhalten wird.
  2. Verfahren nach Anspruch 1, wobei in Schritt (b) das erste Gemisch ferner mit einem Kohlenhydrat, vorzugsweise D-Sorbitol gemischt wird.
  3. Verfahren nach Anspruch 2, wobei das Kohlenhydrat in einer Menge von 5*10-2 bis 2*10-1 molaren Äquivalenten vorhanden ist, vorzugsweise von 8*10-2 bis 1,2*10-1 molaren Äquivalenten.
  4. Verfahren nach einem der vorangehenden Ansprüche, das bei Raumtemperatur durchgeführt wird.
  5. Verfahren nach einem der vorangehenden Ansprüche, wobei die in Schritt (e) erhaltene Lösung klar ist.
  6. Verfahren nach einem der vorangehenden Ansprüche, wobei der Titanoxidvorläufer ein Titanalkoxid, vorzugsweise ein Titan(IV)alkoxid der allgemeinen Formel (II):

            Ti(OR)4     (II)

    ist, wobei R aus C1-C4 linearen Alkyl- oder C3-C4 verzweigten Alkylketten ausgewählt ist.
  7. Verfahren nach einem der vorangehenden Ansprüche, wobei der Titanoxidvorläufer Titan(IV)isopropoxid ist.
  8. Verfahren nach einem der vorangehenden Ansprüche, wobei der wassermischbare Alkohol die allgemeine Formel

            R-OH     (III)

    hat, wobei R aus C1-C3 linearen Alkyl- und C3 verzweigten Alkylgruppen ausgewählt ist.
  9. Verfahren nach Anspruch 8, wobei der wassermischbare Alkohol Ethanol ist.
  10. Verfahren nach einem der vorangehenden Ansprüche, wobei die Säure eine organische Säure ist, die vorzugsweise die allgemeine Formel (IV)

            R-COOH     (IV)

    hat, wobei R aus C1-C4 linearen Alkyl- oder C3-C4 verzweigten Alkylketten ausgewählt ist.
  11. Verfahren nach Anspruch 10, wobei die Säure Essigsäure ist.
EP11154603.2A 2011-02-14 2011-02-16 Elektronentransportierende Titanoxidschicht Active EP2490235B1 (de)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP11154603.2A EP2490235B1 (de) 2011-02-16 2011-02-16 Elektronentransportierende Titanoxidschicht
JP2012008142A JP5845097B2 (ja) 2011-02-14 2012-01-18 電子輸送チタン酸化物層
US13/358,929 US20120207947A1 (en) 2011-02-14 2012-01-26 Electron transporting titanium oxide layer
KR1020120014438A KR101876575B1 (ko) 2011-02-14 2012-02-13 전자수송용 산화티타늄층

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EP11154603.2A EP2490235B1 (de) 2011-02-16 2011-02-16 Elektronentransportierende Titanoxidschicht

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EP2490235A1 EP2490235A1 (de) 2012-08-22
EP2490235B1 true EP2490235B1 (de) 2014-04-02

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US9985231B2 (en) * 2015-02-25 2018-05-29 Nutech Ventures, Inc. Compositionally graded bulk heterojunction devices and methods of manufacturing the same
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JP6906210B2 (ja) 2019-10-08 2021-07-21 Ｊｆｅスチール株式会社 積層体、有機薄膜太陽電池、積層体の製造方法および有機薄膜太陽電池の製造方法

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JP3080162B2 (ja) * 1998-01-27 2000-08-21 日本パーカライジング株式会社 酸化チタンゾルおよびその製造方法
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US7255847B2 (en) * 2004-11-16 2007-08-14 The Hong Kong Polytechnic University Method for making single-phase anatase titanium oxide
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TW200744679A (en) * 2006-06-09 2007-12-16 Atomic Energy Council Plasma preparation method for containing titanium dioxide of multifunctional polymeric biomaterial
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US20120207947A1 (en) 2012-08-16
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